Disazo fiber reactive dyestuffs

ABSTRACT

A compound of Formula (1) and salts thereof. ##STR1## wherein: A is optionally substituted phenyl; 
     E is optionally substituted phenylene; 
     R 1  is H or optionally substituted alkyl; 
     R 2  is H or optionally substituted alkyl and 
     R 3  is H, optionally substituted alkyl, optionally substituted alkoxy or optionally substituted aryl, or 
     R 2  and R 3  taken together with the N atom to which they, are attached from an optionally substituted piperidine or morpholine ring; 
     Q is optionally substituted pyridinium; and 
     m is 0 or 1.

This application claims benefit of international applicationPCT/GB95/00083, filed Jan. 18, 1995.

This invention relates to organic chemicals, in particular to reactivedyes, their preparation and use.

According to the present invention there is provided a compound ofFormula (1) and salts thereof: ##STR2## wherein: A is optionallysubstituted phenyl;

E is optionally substituted phenylene;

R¹ is H or optionally substituted alkyl;

R² is H or optionally substituted alkyl and

R³ is H, optionally substituted alkyl, optionally substituted alkoxy oroptionally substituted aryl, or

R² and R³ taken together with the N atom to which they are attached froman optionally substituted piperidine or morpholine ring;

Q is optionally substituted pyridinium; and

m is 0 or 1.

The optional substituents which may be present on A, E, R¹, R², R³ and Qare preferably selected from halo, especially chloro; nitro; C₁₋₄-alkyl; C₁₋₄ -alkoxy; sulpho; carboxy; carbonamido; acylamino,especially acetamido; ureido; hydroxy; phosphato; sulphato; and amino.

A is preferably unsubstituted phenyl or phenyl having 1 or 2substituents. When A is substituted it is preferred that it has at leastone sulpho substituent. In an especially preferred embodiment A is4-sulphophenyl.

Examples of groups represented by A include 2-, 3- and 4-sulphophenyl;4-carboxy-2-sulphophenyl; 2,4-disulphophenyl; 2,5-disulphophenyl;3,5-disulphophenyl; 2-sulpho-4-methoxyphenyl; 2-sulpho-4-methylphenyl;3-nitrophenyl; 2-methoxy-4-sulphophenyl; 2-methyl-4-sulphophenyl;4-chloro-2-sulphophenyl; and 2,5-dichloro-4-sulphophenyl.

E is preferably optionally substituted 1,4-phenylene, especially1,4-phenylene which is unsubstituted or substituted by 1 or 2 of theaforementioned optional substituents, preferably by 1 or 2 groupsselected from halo, sulpho, C₁₋₄ -alkoxy and C₁₋₄ -alkyl- When E issubstituted it preferably has at least one sulpho substituent.

R¹ is preferably H or C₁₋₄ -alkyl, more preferably C₁₋₄ -alkyl,especially methyl or ethyl. The preference for R¹ being C₁₋₄ -alkylarises from the surprising finding that this can lead to improvedwash-off properties in the dye.

R² is preferably H, optionally substituted C₁₋₄ -alkyl, more preferablyH or C₁₋₄ -alkyl, especially methyl or ethyl.

R³ is preferably H, optionally substituted alkyl, optionally substitutedphenyl or C₁₋₄ -alkoxy, more preferably H, optionally substituted C₁₋₄-alkyl, phenyl or sulphophenyl, especially H, methyl or ethyl.

Examples of groups represented by R² and R³ include --CH₃, --CH₂ CH₃,--CH₂ CH₂ OH, --CH₂ CH₂ CO₂ H, --CH₂ CH₂ SO₃ H, --CH₂ CH₂ OSO₃ H,--(CH₂)₃ CO₂ H, --CH₂ CO₂ H, --CH₂ PO₃ H₂, --CH(CO₂ H)CH₂ CO₂ H,--CH(CO₂ H)CH₂ CH₂ CO₂ H, 4- sulphophenyl, 3-sulphophenyl, 2,5- and2,6-disulphophenyl, --OCH₃ and --(CH₂)₂ CH₃.

Preferably R² and R³ are free from groups which, on treatment withaqueous alkali, yield groups of formula --SO₂ CH═CH₂. Thus R² and R³preferably do not contain groups of formula --SO₂ CH₂ CH₂ OSO₃ H, --SO₂CH₂ CH₂ Cl or salts thereof.

In one preferred embodiment R² and R³ are each independently H, C₁₋₄-alkyl or C₁₋₄ -alkyl having an --OH group, or R² and R³ taken togetherwith the N atom to which they are attached form an optionallysubstituted piperidine or morpholine ring. Such compounds haveparticularly good build-up in exhaust dyeing.

Q is preferably pyridinium having 1 or 2 substituents selected fromcarboxy, C₁₋₄ -alkyl and carbonamido (i.e. CONH₂). Examples of groupsrepresented by Q include 3- and 4-carboxypyridinium, pyridinium,3-methylpyridinium , 3- and 4-carbonamidopyridinium .

The --NR¹ -- group shown in Formula (1) is preferably at the 6- positionon the naphthalene ring relative to the hydroxy group. When the --N¹ --group shown in Formula (1) is at the 6-position on the naphthalene ringrelative to hydroxy group it is preferred that m has a value of 0.

The compound is preferably in salt form, for example in the form of asodium, lithium, potassium, ammonium or substituted ammonium salt or amixture thereof.

It is preferred that compounds of Formula (1) are free from groupswhich, on treatment with aqueous alkali, yield --SO₂ CH═CH₂ groups.

Compounds of Formula (1) wherein Q is optionally substituted pyridiniummay be prepared by condensing the corresponding compound wherein Q ishalo (preferably Cl or F) with an optionally substituted pyridinecompound, preferably in aqueous medium. Elevated temperatures arepreferred for the condensation, for example 60° C. to 110° C., and atime of 1 to 24 hours normally suffices. A pH of 5 to 8 may be used.

The compound of Formula (1) wherein Q is halo may be prepared bycondensing one equivalent of an amine of formula HNR² R³ with a compoundof Formula (1) wherein both of the triazine substituents shown on theright hand side are halo. The compound of Formula (1) wherein both ofthe triazine substituents shown on the right hand side are halo may beprepared by condensing cyanuric halide with a compound of Formula (2)(wherein A, E, R¹ and m are as hereinbefore defined), preferably in anaqueous medium, preferably at a pH in the range 5 to 7: ##STR3##

The compounds of Formula (2) may be prepared by azo chemistry analogousto that known in the dyestuff art, for example by diazotising an amineA--N═N--E--NH₂ at below 5° C. using a diazotising agent (e.g. NaNO₂/mineral acid) and coupling onto the desired hydroxy naphthalenecompound, which may have the --NHR¹ group protected if so desired.

The compound of Formula (1) wherein both of the triazine substituentsshown on the right hand are halo may also be prepared by diazotising anamine of Formula (3) and coupling onto a compound of Formula (4):##STR4## wherein A, E, R¹ and m are as hereinbefore defined. Thediazotisation is preferably performed below 5° C., preferably in aqueousmedium, preferably in the presence of NaNO₂ and mineral acid.

According to a further feature of the invention there is provided aprocess for the coloration of a substrate comprising applying thereto acompound according to the invention.

The preferred substrate contains hydroxyl and/or amino groups, and ispreferably a textile material, a leather or a paper. Preferred textilematerials are wool, silk, synthetic polyamides and especially cellulosicmaterials, particularly cotton, jute, hemp and flax.

Preferred coloration processes include exhaust, pad batch, continuousand semi-continuous dyeing and printing, especially exhaust dyeing.

The coloration process for cellulosic textile substrates is preferablyperformed using a solution of the dye in water. An acid binding agent isnormally used in the process for colouring cellulosic substrates. Thisagent may be applied to the cellulosic textile before, during or afterapplication of the compound. Suitable acid binding agents include NaOH,NaHCO₃ and Na₃ CO₃.

A further feature of the invention provides a substrate coloured by thecoloration process or using a dye according to the invention.

The compounds of the invention wherein Q is optionally substitutedpyridinium (particularly 3- or 4-carboxypyridinium) are notable fortheir good dyeing properties, particularly in exhaust dyeingapplications. The compounds dye cellulosic materials strong brightshades, demonstrating good build-up and good wash-off properties. Thecompounds also benefit from compatibility with existing PROCION™ H-EXL™reactive dyes of different shades, thereby enabling binary and ternarymixtures to be prepared which dye in a highly reproducible manner undera variety of different conditions (PROCION™ dyes are available fromZENECA Specialties, Manchester, England).

The invention is further illustrated but not limited by the followingexamples in which all parts and percentages are by weight unlessotherwise indicated.

EXAMPLE 1

Preparation of ##STR5## Stage a

4-Aminoazobenzene-3,4¹ -disulphonic and (52.3 g, 0.137M) was dissolvedin dilute NaOH solution to give a solution of pH 7.5. 2N Sodium nitritesolution (71 ml, 0.142M) was added and the resulting solution was addeddropwise, with stirring, to a mixture of ice/water (500 ml) containingconcentrated hydrochloric acid (50 ml). The mixture was stirred for 45minutes at <5° C., excess nitrous acid was destroyed (by addingsulphamic acid) and a solution of3-hydroxy-6-acetylaminonaphthalene-3-sulphonic acid (MI 343, 47 g,0.137M) was added. The pH was raised slowly to 2.5 using potassiumacetate and the mixture stirred at <5° C. for 30 minutes, then at pH 3and temperature <5° C. and finally stirred at pH 4.5. Salt solution (25%w/v) was added and the precipitated solid collected. The damp solid wasadded to hot water (2.5l) to give a gel, the pH was raised to 7.0 usingNaOH solution (70°,Tw) then sodium hydroxide (100 g) was added slowly,the mixture was stirred at 75° to 85° C. for 3 hours, salt solution (330g, 15% w/v) was added to the hot solution and heating discontinued. Oncooling the precipitated solid was collected to give 105 g (56% at MI1377) of 1-Hydroxy-2-4-(4"-sulphophenylazo)-2'-sulphophenylazo!-6-aminonaphthalene-3-sulphonicacid.

Stage b

A solution of cyanuric chloride (7.4 g, 0.04 M) in acetone (70 ml) wasadded to a stirred mixture of the product from Stage a) (50 g, MI 1377,0.036M) in ice/water (500 ml) containing a few drops of calsolene oil.The mixture was stirred at below 5° C., pH 6.5, for 2 hours. Furthercyanuric chloride (3.5 g) was added and stirring continued at pH 6.5,0-5° C., for a further 1 hour, after which HPLC indicated that reactionwas essentially complete. The mixture was filtered to remove a smallamount of undesirable insoluble material.

Stage c

N-methylaniline (2.14 g, 0.02M) was added to half of the productresulting from Stage b) and the mixture stirred at 50° C. and pH 6.5.After 2 hours more N-methylaniline (1.0 g) was added and the heating at50° C. and pH 6.5 was continued for a further 1 hour. Thedichlorotriazinyl product precipitated and was collected.

Stage d

4-Carboxy pyridine (12.3 g, 0.1M) was added to a mixture of the productfrom Stage c) and water (500 ml) and the pH adjusted to 6.5 using sodiumcarbonate solution (2N). The mixture was heated under reflux for 15hours and allowed to cool to room temperature. The precipitated sodiumisonicotinate was filtered-off and ethanol (740 ml) added to the stirredfiltrate. The precipitated product was collected and dried to give thetitle product (12.0 g, MI 1181, 51% yield) having a λmax (water) at535.4 nm.

The title product was applied to cotton by exhaust dyeing at 80° C. andthe cotton was dyed a bright red shade, showing good fixation.

EXAMPLE 2

Preparation of ##STR6##

The method of Example 1 was followed except that in Stage c)4-sulpho-N-methylaniline was used in place of N-methylaniline. The titleproduct had a λmax at 534 nm (water).

The title product was applied to cotton by exhaust dyeing to give abright yellowish-red shade, showing excellent build-up and fixation.

EXAMPLE 3

Preparation of ##STR7##

The method of Example 1 was repeated except that in Stage a), in placeof 1-hydroxy-6-acetylaminonapthalene-3-sulphonic acid there was used1-hydroxy-6-N-acetylmethylaminonaphthalene-3-sulphonic acid. The titleproduct was found to have a λmax of 530.5 nm (water).

The title product was applied to cotton by exhaust dyeing to give abright red shade, showing good build-up, high fixation and goodwash-off.

EXAMPLE 4

Preparation of ##STR8##

The method of Example 3 was followed except that4-sulpho-N-methylaniline was used in place of N-methylaniline. The titleproduct had a λmax at 518 nm (water).

The title product was applied to cotton by exhaust dyeing to give abright yellowish-red shade showing good build-up and wash-off.

EXAMPLES 5 to 34

Dyes of Formula (5) described in Table 1 below were prepared using ananalogous process to that described in Example 1: ##STR9##

                                      TABLE 1                                     __________________________________________________________________________                                  Position                                                                            λmax                               Example                                                                            R.sup.2       R.sup.3    of --CO.sub.2 H                                                                     (nm)                                      __________________________________________________________________________    5    --CH.sub.3    4-sulphophenyl                                                                           4     516                                       6    --CH.sub.2 CO.sub.2 H                                                                       --CH.sub.3 4     514                                       7    --CH.sub.3    --CH.sub.3 4     517                                       8    --H           2,5-disulphophenyl                                                                       4     517                                       9    --H           --CH.sub.2 CH.sub.2 OH                                                                   4     515                                       10   --CH.sub.2 CH.sub.2 OH                                                                      --CH.sub.2 CH.sub.2 OH                                                                   4     517                                       11   --CH.sub.3    --(CH.sub.2).sub.3 CO.sub.2 H                                                            4     513                                       12   --CH.sub.3    --CH.sub.2 CH.sub.2 OH                                                                   4     530                                       13   --H           --CH.sub.2 CH.sub.2 SO.sub.3 H                                                           4     511                                       14   --H           --CH.sub.2 CH.sub.2 OSO.sub.3 H                                                          4     511                                       15   --CH.sub.3    --H        4     517                                       16   --H           --H        4     515                                       17   --CH.sub.2 CH.sub.3                                                                         --CH.sub.2 CO.sub.2 H                                                                    4     512                                       18   --CH.sub.2 CH.sub.3                                                                         --CH.sub.2 CO.sub.2 H                                                                    3     511                                       19   --CH.sub.2 PO.sub.3 H.sub.2                                                                 --CH.sub.2 CO.sub.2 H                                                                    4     514                                       20   --CH.sub.2 CO.sub.2 H                                                                       --CH.sub.2 PO.sub.3 H.sub.2                                                              3     513                                       21   --H           --CH(CO.sub.2 H)CH.sub.2 CO.sub.2 H                                                      4     512                                       22   --H           --CH(CO.sub.2 H)CH.sub.2 CO.sub.2 H                                                      3     512                                       23   --CH(CO.sub.2 H)CH.sub.2 CH.sub.2 CO.sub.2 H                                                --H        4     512                                       24   --CH(CO.sub.2 H)CH.sub.2 CH.sub.2 CO.sub.2 H                                                --H        3     511                                       25   --H           --H        3     514                                       26   --NR.sup.2 R.sup.3 ═piperidinyl                                                                    4     532                                       27   --NR.sup.2 R.sup.3 ═piperidinyl                                                                    3     530                                       28   --NR.sup.2 R.sup.3 ═morpholinyl                                                                    4     531                                       29   --NR.sup.2 R.sup.3 ═morpholinyl                                                                    3     529                                       30   --CH.sub.2 CH.sub.3                                                                         --CH.sub.2 CH.sub.3                                                                      4     --                                        31   --CH.sub.2 CH.sub.3                                                                         --CH.sub.2 CH.sub.3                                                                      3     --                                        32   --CH.sub.3    --OCH.sub.3                                                                              3     517                                       33   --H           3-sulphophenyl                                                                           3     516                                       34   --CH.sub.2 CH.sub.2 CH.sub.3                                                                --CH.sub.2 CH.sub.2 CH.sub.3                                                             3     --                                        __________________________________________________________________________

EXAMPLES 35 to 44

The method of Example 1 may be repeated except that in place of4-carboxy pyridine there is used the pyridine compounds mentioned below:

    ______________________________________                                        Example         Pyridine Compound                                             ______________________________________                                        35              pyridine                                                      36              3-methylpyridine                                              37              3-carbonamidopyridine                                         38              4-carbonamidopyridine                                         39              3-methoxycarbonyl pyridine                                    40              4-methoxycarbonyl pyridine                                    41              3-ethoxycarbonyl pyridine                                     42              4-ethxoycarbonyl pyridine                                     43              4-methyl pyridine                                             44              2-methyl pyridine                                             ______________________________________                                    

EXAMPLES 45 to 58

The method of Example 3 may be repeated except that in place of4-aminoazobenzene-3,4'-disulphonic acid there is used the amine referredto below:

    ______________________________________                                        Example   Amine                                                               ______________________________________                                        45        4-aminoazobenzene-3,3'-disulphonic acid                             46        4-amino-4.sup.1 -sulphoazobenzene                                   47        4-amino-2.sup.1,4.sup.1 -disulphoazobenzene                         48        4-aminoazobenzene-2,5.sup.1 -disulphonic acid                       49        4-aminoazobenzene-3.sup.1 -sulphonic acid                           50        4-amino-2-methylazobenzene-4.sup.1 -sulphonic acid                  51        4-amino-3-methylazobenzene-4.sup.1 -sulphonic acid                  52        4-amino-2-methylazobenzene-5,4.sup.1 -disulphonic acid              53        4-amino-4.sup.1 -methylazobenzene-3,2.sup.1 -disulphonic acid       54        4-amino-2.sup.1 -methylazobenzene-3,4.sup.1 -disulphonic acid       55        4-amino-2-methoxyazobenzene-2.sup.1 -carboxy-5.sup.1                          sulphonic acid                                                      56        4-amino-2-methoxyazobenzene-2.sup.1 -carboxy-4.sup.1 -                        sulphonic acid                                                      57        4-amino-6-acetylaminoazobenzene-2.sup.1,4.sup.1, 3-                           trisulphonic acid                                                   58        4-amino-6-acetylaminoazobenzene-2.sup.1,4.sup.1, 3-                           trisulponic acid                                                    ______________________________________                                    

EXAMPLES 59 to 65

The method of Example 2 may be repeated except that in place of1-hydroxy-6-acetylaminonaphthalene-3-sulphonic acid there is used thenaphthalene compound indicated below:

    ______________________________________                                        Example  Naphthalene Compound                                                 ______________________________________                                        59       1-hydroxy-8-acetylaminonaphthalene-3,6-                                       disulphonic acid                                                     60       1-hydroxy-8-acetylaminonaphthalene-3,5-                                       disulphonic acid                                                     61       1-hydroxy-7-acetylaminonaphthalene-3-sulphonic                                acid                                                                 62       1-hydroxy-7-acetylaminonaphthalene-3,6-                                       disulphonic acid                                                     63       1-hydroxy-7-(N-acetyl)methylaminonaphthalene-3-                               sulphonic acid                                                       64       1-hydroxy-7-(N-acetyl)methylaminonaphthalene-3,6-                             disulphonic acid                                                     65       1-hydroxy-6-acetylaminonaphthalene-3,5-                                       disulphonic acid                                                     ______________________________________                                    

I claim:
 1. A compound of Formula (1) or a salt thereof: ##STR10##wherein: A is phenyl substituted by 1 or 2 sulpho groups and optionallyby C₁₋₄ -alkyl or carboxy;E is optionally substituted phenylene; R¹ is Hor optionally substituted alkyl; R² is H or optionally substituted alkyland R³ is H, optionally substituted alkyl, optionally substituted alkoxyor optionally substituted aryl, orR² and R³ taken together with the Natom to which they are attached form an optionally substitutedpiperidine or morpholine ring; Q is optionally substituted pyridinium;and m is 0 or
 1. 2. A compound according to claim 1 wherein Q ispyridinium having 1 or 2 substituents selected from carboxy, C₁₋₄ -alkyland carbonamido.
 3. A compound according to claim 1 wherein Q is 3- or4-carboxypyridinium.
 4. A compound according to any one of the precedingclaims wherein the --NR¹ -- group shown in Formula (1) is at the6-position on the naphthalene ring relative to the hydroxy group.
 5. Acompound according to any one of the preceding claims wherein R³ is H,optionally substituted alkyl or optionally substituted aryl, wherein theoptional substituents are selected from halo, nitro, C₁₋₄ -alkyl, C₁₋₄-alkoxy, sulpho, carboxy, carbonamido, acylamino, ureido, hydroxy,phosphato, sulphato and amino.
 6. A compound according to any one of thepreceding claims wherein R² and R³ are each independently H, C₁₋₄ -alkylor C₁₋₄ -alkyl having a hydroxy group, or R² or R³ taken together withthe N atom to which they are attached form an optionally substitutedpiperidine or morpholine ring.
 7. A compound according to claim 1wherein E is 1,4-phenylene which is unsubstituted or substituted by 1 or2 groups selected from halo, sulpho and C₁₋₄ -alkyl; R¹ is H or C₁₋₄-alkyl; R² is H or optionally substituted C₁₋₄ -alkyl and R³ is H,optionally substituted phenyl or optionally substituted alkyl, or R² andR³ taken together with the N atom to which they are attached form apiperidine or morpholine ring; Q is 3- or 4-carboxypyridinium; the --NR¹-- group shown in Formula (1) is at the 6-position on the naphthalenering relative to the hydroxy group; and m is
 0. 8. A process forpreparing a compound according to claim 1 wherein a compound of Formula(1), as defined in claim 1 except that Q is halo, is condensed with anoptionally substituted pyridine compound.
 9. A process for thecoloration of a substrate comprising applying thereto a compoundaccording to any one of claims 1 to 7.